Classifications

• • C—CHEMISTRY; METALLURGY
  • C07—ORGANIC CHEMISTRY
  • C07D—HETEROCYCLIC COMPOUNDS
  • C07D251/00—Heterocyclic compounds containing 1,3,5-triazine rings
  • C07D251/02—Heterocyclic compounds containing 1,3,5-triazine rings not condensed with other rings
  • C07D251/12—Heterocyclic compounds containing 1,3,5-triazine rings not condensed with other rings having three double bonds between ring members or between ring members and non-ring members
  • C07D251/26—Heterocyclic compounds containing 1,3,5-triazine rings not condensed with other rings having three double bonds between ring members or between ring members and non-ring members with only hetero atoms directly attached to ring carbon atoms
  • C07D251/30—Only oxygen atoms
  • C07D251/34—Cyanuric or isocyanuric esters
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
  • C08G18/00—Polymeric products of isocyanates or isothiocyanates
  • C08G18/02—Polymeric products of isocyanates or isothiocyanates of isocyanates or isothiocyanates only
  • C08G18/022—Polymeric products of isocyanates or isothiocyanates of isocyanates or isothiocyanates only the polymeric products containing isocyanurate groups
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
  • C08G18/00—Polymeric products of isocyanates or isothiocyanates
  • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
  • C08G18/08—Processes
  • C08G18/16—Catalysts
  • C08G18/22—Catalysts containing metal compounds
  • C08G18/225—Catalysts containing metal compounds of alkali or alkaline earth metals
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
  • C08G18/00—Polymeric products of isocyanates or isothiocyanates
  • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
  • C08G18/70—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the isocyanates or isothiocyanates used
  • C08G18/72—Polyisocyanates or polyisothiocyanates
  • C08G18/77—Polyisocyanates or polyisothiocyanates having heteroatoms in addition to the isocyanate or isothiocyanate nitrogen and oxygen or sulfur
  • C08G18/78—Nitrogen
  • C08G18/79—Nitrogen characterised by the polyisocyanates used, these having groups formed by oligomerisation of isocyanates or isothiocyanates
  • C08G18/791—Nitrogen characterised by the polyisocyanates used, these having groups formed by oligomerisation of isocyanates or isothiocyanates containing isocyanurate groups

Definitions

• Isocyanurate bond-forming reaction catalyst and method for producing isocyanurate bond-containing modified polyisocyanate mixture using the same
• the present invention relates to a process for producing an isocyanurate bond-containing modified polyisocyanate mixture used as a high-performance curing agent for two-component polyurethane paints, and an isocyanurate bond-forming reaction catalyst used therefor.
• the isocyanurate bond-containing modified polyisocyanate produced by Toluene diisocyanate (TDI) is excellent in quick-drying and physical properties, and is particularly useful as a polyisocyanate curing agent for coatings.
• a modified polyisocyanate containing isocyanurate bond produced from TDI is desired to have a low content of TDI (monomer) as a raw material from the viewpoint of occupational health when used as a paint. RU
• Patent Document 1 describes a modified polyisocyanate containing an isocyanurate bond containing a solvent having a TDI (monomer) content of 0.1% by mass or less using a mixture of a phenolic catalyst containing a dialkylaminomethyl group. It proposes a simple method for producing the product without distillation.
• Patent Document 1 Japanese Patent Application Laid-Open No. 2004-250662
• Patent Document 1 requires a long time for the reaction to lower the TDI (monomer) content, and as the reaction time becomes longer, the modified polyisoisolate containing an isocyanurate bond. There is a problem in that the content of cyanate is lowered and a high-isocyanate polymer is formed to increase the viscosity.
• An object of the present invention is to provide a process for producing a low polyisocyanate polymer, a isocyanurate bond-containing modified polyisocyanate mixture, and an isocyanurate bond-forming reaction catalyst used therefor.
• the viscosity of the organic polyisocyanate (monomer) is so low that it has no practical problem in terms of occupational health as a curing agent for paints, etc., without performing a purification step by distillation after the reaction.
• Another object of the present invention is to provide a method for efficiently producing a modified polyisocyanate mixture containing an isocyanurate bond in a short time, and an isocyanurate bond-forming reaction catalyst for use in the method.
• the present inventor conducted extensive research on an isocyanurate bond-forming reaction catalyst, and as a result, by using a compound having a specific chemical structure as a catalyst for the isocyanurate bond-forming reaction, The present inventors have found that all the above problems can be solved, and have completed the present invention.
• the present invention includes the following (1) to (10).
• An isocyanurate bond-forming reaction catalyst comprising a compound represented by the following general formula (1):
• M is an alkaline earth metal
• R 1 is an alkyl group having 6 to 10 carbon atoms which may be the same as or different from each other
• n is an integer of 0 or 1.
• the organic polyisocyanate is subjected to an isocyanurate bond-forming reaction in the presence of the isocyanurate bond-forming reaction catalyst according to any one of (1) to (6), and then the reaction is terminated by adding a reaction terminator.
• a process for producing an isocyanurate bond-containing modified polyisocyanate mixture characterized by the following.
• the organic polyisocyanate is subjected to an isocyanurate bond formation reaction in the presence of the isocyanurate bond formation reaction catalyst of any one of (1) to (6), and then the reaction is terminated by adding a reaction terminator.
• the isocyanurate bond-forming reaction is carried out by adding the isocyanurate bond-forming reaction catalyst of (1) dividedly in a plurality of times during the period from the beginning to the end of the isocyanurate bond-forming reaction.
• a method for producing a bond-containing modified polyisocyanate mixture is carried out by adding the isocyanurate bond-forming reaction catalyst of (1) dividedly in a plurality of times during the period from the beginning to the end of the isocyanurate bond-forming reaction.
• a specific isocyanurate bond-forming reaction catalyst is used, and an isocyanate having a low content of organic polyisocyanate (monomer) can be obtained without performing a distillation step. It became possible to produce cyanate mixtures. In particular, a coating that does not require a purification step by distillation after the reaction. As a curing agent such as a coating material, an isocyanurate bond-containing modified polyisocyanate mixture is efficiently produced in a short time with a low organic polyisocyanate (monomer) content and low viscosity so that there is no practical problem in terms of occupational health. It became possible.
• the isocyanurate bond-forming reaction catalyst of the present invention contains a compound represented by the following general formula (1).
• An alkyl cage having 6 to 10 carbon atoms which may be the same or different,
• n is an integer of 0 or 1.
• M is preferably calcium or strontium, and more preferably calcium.
• the compound represented by the general formula (1) when R 1 and R 2 are less than 6 carbon atoms of the alkyl group, the compound represented by the general formula (1) has poor solubility in an organic solvent or an organic polyisocyanate. Sufficient catalytic effect cannot be obtained due to insufficient concentration.
• the compound represented by the general formula (1) when R 1 and R 2 are alkyl groups having 11 or more carbon atoms, the compound represented by the general formula (1) is insoluble in most organic solvents and organic polyisocyanates. It is not suitable for isocyanurate bond formation reaction in a homogeneous system.
• Specific examples of the compound represented by the general formula (1) include bis (dihexylphosphate) calcium, bis (di-n-octylphosphate) calcium, and bis (di-2-ethylhexylphosphate).
• Calcium bis (didecyl phosphate) calcium, bis (dihexyl phosphate) strontium, bis (di-n-octyl phosphate) strontium, bis (di-2-ethylhexyl phosphate) Strontium, bis (didecyl phosphate) strontium, bis (di_2_ethylhexyl phosphate) magnesium, bis (di_2_ethylhexyl phosphate) barium, bis (hex Silylhexyl phosphonate) calcium, bis (n-octynole mono-octyl phosphonate) calcium, bis (2-ethylhexyl 2-ethyl hex
• bis (dioctylphosphate) calcium such as bis (di-1-octylphosphate) calcium and bis (di-2-ethylhexylphosphate) calcium
• bis (n-octyl) _n—octyl phosphonate) calcium bis (2-ethyl hexyl hexyl _2-ethyl hexyl phosphonate) calcium
• the amount of the compound represented by the general formula (1) varies depending on the type of catalyst used, the reaction temperature, etc., but is usually 0.01 to 5% by mass relative to the organic polyisocyanate. It is preferable that it is 1-3 mass%.
• the isocyanurate bond-forming reaction catalyst of the present invention is preferably one in which water is contained in the compound represented by the general formula (1).
• the water content is within 50% by mass with respect to the compound represented by the above general formula (1), and further 0.:! It is preferable to be in the range of ⁇ 20% by mass.
• the isocyanurate bond forming reaction catalyst of the present invention includes, for example, methanol as a promoter. Nore, ethanol, butanol, ethylene glycol, 1,3-butanediol, neopentinoleglycolanol, 2-ethyl-1,3-hexanediol, trimethylolpropane, polypropylene glycol, phenol, any two or more of these It is preferable to further contain a hydroxyl group-containing organic compound such as a mixture of
• the promoter is used before the isocyanurate bond forming reaction step, when it is not included in the promoter power S isocyanurate bond forming reaction catalyst.
• it can be used together with an isocyanurate bond-forming polymerization catalyst, or before adding an isocyanurate bond-forming polymerization catalyst, it is reacted with an organic polyisocyanate described later in advance to form a urethane group. Also good.
• the isocyanurate bond-forming reaction catalyst of the present invention can be used by dissolving the compound represented by the general formula (1) and, if necessary, a promoter in a solvent.
• solvents include pentane, hexane, heptane, octane, cyclopentane, cyclohexane, decahydronaphthalene, petroleum ether, petroleum benzine, kerosene, mineralol spirit, jetyl ether, tetrahydrofuran, ethyl acetate, butyl acetate, and acetone.
• Methyl ethyl ketone, methyl isobutyl ketone, toluene, xylene, tri (2-ethylhexyl) phosphate, and mixtures of any two or more of these solvents are inert to the isocyanate group.
• organic polyisocyanate used in the method for producing the isocyanurate bond-containing modified polyisocyanate mixture of the present invention include 2, 4-TDI, 2, 6-TDI, Xylene 1,4-diisocyanate, xylene 1,3-diisocyanate, tetradiphenylmethane diisocyanate, 4, 1-diphenyl ether diisocyanate, 2 —nitrodiphenyl 4,4 'A ′ —diisocyanate, 2, 2'—Diphenylpropane-1,4,4′—Diisocyanate, 3, 3 r —Dimethyldiphenylmethane-1,4,4 ; —Diisocyanate, 4,1, Diphenylpropanediisocyanate, m—Phenylene range Isoshianeto, p - phenylenediamine iso Xia sulfonate, naphthylene one 1, 4-J
• examples thereof include alicyclic diisocyanates such as nilmethane diisocyanate and hydrogenated tetramethylxylene diisocyanate, and a mixture of any two or more of these.
• TDI is more preferred, 2,4-TDI alone or a mixture of 2,4-TDI and 2,6-TDI.
• organic polyisocyanates may contain an antioxidant described later.
• triphenyl phosphite trisnoylphenyl phosphite, tricresyl can be used as necessary during the isocyanurate bond forming reaction.
• a solvent can be used as necessary during the isocyanurate bond forming reaction.
• the solvent include solvents that are inert to isocyanate groups such as ethyl acetate, butyl acetate, isobutyl acetate, acetone, methyl ethyl ketone, methyl isobutyl ketone, toluene, xylene, and a mixture of any two or more thereof.
• the isocyanurate bond forming reaction is generally performed at 150 ° C in the presence of an organic polyisocyanate in the presence of an isocyanurate bond forming reaction catalyst.
• the reaction is preferably carried out at 20 to 120 ° C., generally within 50 hours, preferably 10 minutes to 15 hours, until a predetermined isocyanate group content (hereinafter referred to as NCO content) is reached.
• NCO content a predetermined isocyanate group content
• the isocyanurate bond formation reaction is preferably performed at a low temperature because the content of the organic polyisocyanate (monomer) at the end of the isocyanurate bond formation reaction can be reduced.
• examples of the terminator for the isocyanurate bond formation reaction include phosphoric acid, sulfuric acid, hydrochloric acid, acetic acid, trifluoroacetic acid, ⁇ _toluenesulfone. Acids such as acids, benzenesulfonic acid, acid chlorides such as dialkyl phosphates, dialkyl phosphonates, benzoyl chloride, acetyl, or a mixture of any two or more of these.
• acids particularly phosphoric acid are preferred.
• the amount of the isocyanurate bond-forming reaction terminator used is preferably 1 to 2 times the equivalent of neutralizing the compound represented by the general formula (1).
• the terminator for the isocyanurate bond forming reaction can be used by dissolving in a solvent.
• the solvent include petroleum ether, petroleum benzine, tetrahydrofuran, ethyl acetate, butyl acetate, acetone, methyl ethyl ketone, methyl isobutyl ketone, toluene, xylene, and any isocyanate group such as a mixture of any two or more thereof. And inert solvents.
• an isocyanurate bond formation reaction terminator is added, Treatment is generally carried out at 20 to 120 ° C, preferably 40 to 80 ° C, generally for 15 minutes to 3 hours, preferably 30 minutes to 1.5 hours to stop the isocyanurate bond formation reaction.
• the organic polyisocyanate (monomer) content in the reaction product isocyanurate bond-containing modified polyisocyanate mixture is 0.5 mass in order to fully exhibit the above performance and to improve the working environment. % Or less is preferable.
• the isocyanurate bond-containing modified polyisocyanate mixture obtained by the present invention comprises: In addition to paints for woodwork, metal, plastics, etc., adhesives, pressure sensitive adhesives, adhesives, synthetic leather, magnetic recording material binders, foams, flooring, molded products, waterproofing materials, anchoring agents, etc. However, it is preferably used especially for woodwork paints.
• the isocyanurate bond-containing modified polyisocyanate mixture obtained by the present invention is used as a two-component polyurethane paint, it is combined with a polyvalent hydroxyl compound containing two or more active hydrogens that react with isocyanate.
• a polyvalent hydroxyl compound containing two or more active hydrogens that react with isocyanate preferable.
• Specific examples include saturated or unsaturated polyester polyols, saturated or unsaturated oil-modified or fatty acid-modified alkyd polyols, amino alkyd polyols, polycarbonate polyols, acryl polyols, polyether polyols, epoxy polyols, polystrength prolataton diols, Used in combination with fluorine-containing polyols, silicone-containing polyols, urea resins and the like. These may be further combined with compounds having active hydrogen groups other than hydroxyl groups such as polyamines and polyamides.
• the polyurethane paint includes known additives such as colorants, extender pigments, fiber bases, leveling agents, antifoaming agents, anti-sagging agents, urethanes. Catalysts, organic solvents, diluents, plasticizers and the like can be added.
• Di (2-ethylhexyl) phosphate 32.2 g (0.1 mol) was dissolved in 75 g of petroleum benzine and placed in a separatory funnel.
• 3.7 g (0.05 mol) of calcium hydroxide was suspended in 50 g of water, and slowly added to the separatory funnel while paying attention to heat generation.
• the separatory funnel was shaken well to sufficiently mix the aqueous phase and the organic phase, and then left for about 5 minutes.
• 3. Og (0.04 mol) of calcium hydroxide was added to the separatory funnel as a powder and shaken well to mix. It was allowed to stand until the aqueous phase and the organic phase were separated, and it was confirmed that the pH of the aqueous phase was 10 or more.
• the aqueous phase was discarded and the cloudy organic phase was transferred to a sample bottle and allowed to stand at room temperature for several days to precipitate a white suspension. .
• the supernatant liquid was taken out and the solvent was removed therefrom to obtain a white solid of bis (di-2-ethylhexyl phosphate) calcium.
• Di (2-ethylhexyl) phosphate 32.2 g (0.1 mol) was dissolved in 97 g of petroleum benzine and placed in a separatory funnel.
• 3.7 g (0.05 mol) of calcium hydroxide was suspended in 50 g of water, and slowly added to the separatory funnel while paying attention to heat generation.
• the separatory funnel was shaken well to sufficiently mix the aqueous phase and the organic phase, and then left for about 5 minutes.
• 3.0 g (0.04 mol) of calcium hydroxide was added to the separatory funnel as a powder and mixed by shaking well. It was allowed to stand until the aqueous phase and the organic phase were separated, and it was confirmed that the pH of the aqueous phase was 10 or more.
• a white solid of bis (di_2-ethylhexylphosphate) barium was obtained in the same manner as in Synthesis Example 4 except that 31.6 g (0.lmol) of barium hydroxide was used instead of strontium hydroxide. .
• a white solid of di (2-ethylhexyl) phosphate was obtained in the same manner as in Synthesis Example 6 except that 6.2 g (0. l mol) of potassium hydroxide was used instead of sodium hydroxide. .
• trimer form Manufacture of modified polyisocyanate mixture containing isocyanurate bond (hereinafter referred to as trimer form)]
• trimer form Manufacture of modified polyisocyanate mixture containing isocyanurate bond
• trimer form In a reaction vessel equipped with a stirrer, a thermometer and a reflux condenser, toluene diisocyanate (2, 4 —TDI and 2, 6—TDI and 80Z20 mixture, Nippon Polyurethane Industry Co., Ltd.
• the heater was removed, the reaction vessel was kept at 55 to 65 ° C. while cooling with water, and when the heat generation stopped, the heater was attached, and the mixture was stirred at the same temperature for about 2.5 hours to carry out the isocyanurate bond formation reaction.
• 0.6 g of a 30% solution of phosphoric acid (manufactured by Kishida Chemical Co., Ltd.) dissolved in butyl acetate was added as a terminator for the isocyanurate bond formation reaction.
• the isocyanurate bond formation reaction was stopped by stirring at ⁇ 65 ° C for 1 hour.
• Example 1 2.5% bis (di_2-ethylhexylenophosphate) calcium solid obtained in Synthesis Example 1 1.
• Use 2.4 g instead of 2 g, and use phosphoric acid Trimer body was prepared in the same manner except that 1.2 g was used instead of 0.6 g and the isocyanurate bond formation reaction was carried out for 1.5 hours using 0.6 g of butyl acetate solution (phosphate / butyl acetate 3Z7) .
• Heng P-360 0.5g And 3,5-di-t_butyl _4-hydroxytoluene (Yoshinox BHT manufactured by Yoshitake Pharmaceutical Co., Ltd.) 0.5g, and the inside of the container was purged with nitrogen, and the reaction solution was heated to 60 ° C while stirring. Heat generation started approximately 20 minutes after reaching 60 ° C. The heater was removed, and the reaction vessel was kept at 55 to 65 ° C. with water cooling, and stirred for about 0.5 hours to carry out the isocyanurate bond formation reaction. When the heat sinks, attach a heater and stir at 55 to 65 ° C for an additional 1.5 hours before synthesis.
• Example 1 instead of toluene diisocyanate (80/20 mixture of 2,4-TDI and 2,6-TDI, Coronate T-80 manufactured by Nippon Polyurethane Industry Co., Ltd.), 500 g of toluene diisocyanate (2, 4_TDI, manufactured by Nippon Polyurethane Industry Co., Ltd.), and 500 g of bis (di_2-ethylhexyl phosphate) calcium solid with a water content of 2.5% obtained in Synthesis Example 1 1.2 g Instead of bis (di-2-ethylhexylphosphine obtained in Synthesis Example 2 G) A trimer was prepared in the same manner except that 4.4 g of a 27.5% petroleum benzine solution of calcium was used for 3.5 hours for the isocyanurate bond formation reaction.
• toluene diisocyanate 80/20 mixture of 2,4-TDI and 2,6-TDI, Coronate T-80 manufactured by Nippon Polyurethane Industry Co., Ltd
• Example 1 2.5% bis (di_2-ethylhexylenophosphate) calcium solid obtained in Synthesis Example 1 1.2% in place of 2g Moisture content obtained in Synthesis Example 3 0.2 % Solids of bis (di_2_ethylhexyl phosphate) calcium 4.
• a trimer was prepared in the same manner except that 2. Og was used and an isocyanurate bond formation reaction was performed for 3.5 hours.
• toluene diisocyanate 80/20
• Example 1 instead of toluene diisocyanate (80/20 mixture of 2,4-TDI and 2,6-TDI, Coronate T-80 manufactured by Nippon Polyurethane Industry Co., Ltd.), 500 g of toluene diisocyanate (2, 4_TDI, manufactured by Nippon Polyurethane Industry Co., Ltd.) Using 500 g of bis (di_2_ethylhexyl phosphate) calcium solid with a moisture content of 2.5% obtained in Synthesis Example 1 instead of 2 g The solid content of bis (di-2-ethylhexyl phosphate) barium with a moisture content of 11% obtained in Synthesis Example 5 was used. ) Instead of 0.6 g (4. 2 g was used to prepare a trimer body in the same manner except that 45.0 Nichiji ⁇ isocyanurate bond formation reaction was performed.
• Example 1 2.5% bis (di_2-ethylhexylenophosphate) calcium solid obtained in Synthesis Example 1 1.
• Use Og and butyl acetate solution of phosphoric acid (Phosphate / Butyl acetate 3Z7) 1.
• Use Og instead of 0.6 g Trimeric bodies were produced in the same manner except that the time isocyanurate bond formation reaction was performed.
• Example 1 2.5% bis (di-2-ethylhexylenophosphate) calcium solid content obtained in Synthesis Example 1 1.
• Use 5 g and also use butyl acetate solution of phosphoric acid (phosphoric acid / butyl acetate 3/7) 1.
• a trimer was produced in the same manner except that the bond formation reaction was performed.
• Example 1 the solid content of bis (di-2-ethylhexylenophosphate) calcium having a water content of 2.5% obtained in Synthesis Example 1 1.
• White kerosene solution of calcium 2-ethylhexanoate instead of 2 g (Made by Nippon Chemical Industry Co., Ltd.) 3.
• Use 3g, and use butyl acetate solution of phosphoric acid (phosphate Z-butyl acetate 3/7) 1.
• Example 1 Toluene diisocyanate (80/20 mixture of 2,4-TDI and 2,6-TDI, Coronate T-80 manufactured by Nippon Polyurethane Industry Co., Ltd.) Using 2.5 g of isocyanate (2, 4-TDI, manufactured by Nippon Polyurethane Industry Co., Ltd.), 2.5% bis (di-2-ethylhexyl phosphate) calcium solid obtained in Synthesis Example 1 1. Water content obtained in Synthesis Example 6 instead of 2 g 1.5% solid of di (2-ethylhexyl) phosphate sodium 1.
• Example 1 instead of 500 g of toluene diisocyanate (80/20 mixture of 2,4-TDI and 2,6-TDI, Coronate T-80 manufactured by Nippon Polyurethane Industry Co., Ltd.) 4_TDI, manufactured by Nippon Polyurethane Industry Co., Ltd.) Using 500 g of bis (di_2_ethylhexyl phosphate) calcium solid with a moisture content of 2.5% obtained in Synthesis Example 1 instead of 2 g Moisture content obtained in Synthesis Example 7 1. 1% di (2-ethylhexyl) phosphate potassium solid 1.
• T D I trimer body consisting of (TD I 3) child with respect to solid content in reaction product by GPC analysis, and containing one isocyanurate bond in S child
• TD I pentamer Reaction product by GPC analysis
• the content of TD I pentamer is composed of (TD I 5) molecules for the solid content in J3 ⁇ 4 l and contains two isocyanurate bonds in the molecule)
• Viscosity (mPa ⁇ s / 25.C) 2100 2300

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